The construction and control of 2D layered molecular packing motifs with functionally substituted π-electron cores are crucial for developing organic electronic materials and devices. We investigated a regioisomeric structure-property relationship in high-performance and solution-processable layered organic semiconductors based on mono-octyl-substituted benzothieno[3,2-b]naphtho[2,3-b]thiophene (mono-C8-BTNT). We demonstrated that an isomorphous bilayer-type layered herringbone packing motif is obtainable in a series of four positional isomers of mono-C8-BTNTs whose π-electron core is substituted by an octyl chain at one of the four most peripheral positions with roughly keeping the rod-like molecular shape. These regioisomeric compounds exhibited systematic variations in the solvent solubility and liquid-crystalline phase transitions at elevated temperatures. The analysis of intermolecular interaction energies in the crystals based on dispersion-corrected DFT calculations revealed that the crystals of 2- and 8-mono-C8-BTNTs are more stable than those of 3- and 9-mono-C8-BTNTs owing to the higher ordering of alkyl chain layers in the crystals. Such differences of the stability in their crystal formation are closely correlated with TFT performances, where the single-crystal devices of the 2- and 8-mono-C8-BTNTs substituted at the most peripheral positions exhibit high-performance TFT characteristics with a mobility of approximately 10 cm2 V-1 s-1.
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